JP2015501534A - Solution-processed nanoparticle-nanowire composite film as a transparent conductor for electro-optic devices - Google Patents

Abstract

The present invention provides a nanoparticle-nanowire composite film by a solution process as a transparent conductor for an electro-optical device. An electro-optical device includes a substructure and a joint portion electrically connected at an overlapping portion of the nanowires, and the substructure is formed to form a network of nanowires defining a space without the nanowires. A layer of nanowires deposited thereon and a plurality of said spaces arranged to at least partially fill and form a further conductive path for said network of nanowires traversing said spaces and light transmission A plurality of nanoparticles having properties. The network of nanowires and the plurality of nanoparticles having electrical conductivity and optical transparency form at least a part of the optically transparent electrode of the electro-optical device. [Selection] Figure 1

Description

(Refer to related applications)
This application claims priority from US Provisional Application No. 61 / 546,659, filed Oct. 13, 2011, the entire contents of which are hereby incorporated by reference.

  The presently claimed technical field according to embodiments of the present invention relates to an electro-optical device and a manufacturing method thereof, and more particularly, to an electro-optical device having a nanoparticle-nanowire composite transparent electrode and a manufacturing method thereof.

  Currently, the most widely used transparent conductive film for electro-optical devices such as liquid crystal displays, touch screen displays and solar cells is, for example, indium tin oxide (hereinafter referred to as “ITO”). (The terms “electro-optic” and “opto-electronic” are used interchangeably.) ITO is widely applied in many fields because of its high transparency and low sheet resistance. Has been. Although ITO has been in use for decades, there has been a great deal of interest in developing ITO alternatives as indium has become more difficult to obtain and the price has increased accordingly. In recent years, there has been an urgent demand for new transparent electrodes against the background of the further increase in demand for such transparent electrodes and the limited supply of indium.

  There are several candidates for transparent electrodes based on materials that have the potential to replace ITO. For example, there are those using carbon nanotubes (hereinafter referred to as “CNT”), graphene, or a thin metal film. However, all these candidates have the disadvantage that they do not achieve both light transmission and electrical conductivity.

  In recent years, efforts have been made to form a transparent conductor using a silver nanowire (hereinafter referred to as “AgNW”) network. However, some unsolved problems remain in mass production of AgNW films. First, in order to achieve high conductivity, sufficient electrical connection between crossed AgNWs is an important factor. However, due to the surface active coating of PVP on the AgNW surface, an extra step to fuse the crossed AgNW often occurs. Such processes include high temperature thermal annealing (> 150 ° C.), application of excess pressure or vacuum filtration to an anodized aluminum (hereinafter “AAO”) film substrate, and HCl vapor treatment. Second, in order to obtain an AgNW fibrous film having stability and robustness, a strong adhesive force is required between the AgNW and the substrate. In order to improve the adhesion of AgNW to the substrate, a method for modifying the surface of the substrate is employed. A strong adhesion force between the AgNW and the substrate can also be obtained by a method of embedding the AgNW in the polymer film by applying pressure. Furthermore, it has been reported that the adhesion can be improved by nail polish or in-situ polymerization method. However, in these efforts, a transparent electrode that can sufficiently replace ITO and a manufacturing method thereof have not been obtained yet. Accordingly, there remains a need for improved transparent electrodes, methods for manufacturing the electrodes, and devices using the electrodes.

  An electro-optical device according to an embodiment of the present invention has a substructure and a joint electrically connected at a portion where nanowires overlap, and forms a network of nanowires that partitions a space without the nanowires A layer of nanowires deposited on the substructure and a conductor arranged to at least partially fill a plurality of the spaces and form a further conducting path for the network of nanowires across the spaces And a plurality of nanoparticles having light permeability. The network of nanowires and the plurality of nanoparticles having electrical conductivity and light permeability form at least a part of the light transmissive electrode of the electro-optical device.

  An electro-optical device manufacturing method according to an embodiment of the present invention includes a step of preparing a lower structure, a joint electrically connected at a portion where nanowires overlap, and a nanowire that partitions a space without the nanowire Depositing a layer of nanowires on the substructure to form a network of, and forming at least a plurality of the spaces to form additional conductive paths for the network of nanowires across the spaces. Depositing a plurality of electrically conductive and light transmissive nanoparticles on the substructure and the layer of nanowires to partially fill. The network of nanowires and the plurality of nanoparticles having electrical conductivity and light permeability form at least a part of the light transmissive electrode of the electro-optical device.

  An electro-optical device manufacturing method according to an embodiment of the present invention includes a step of preparing a lower structure, a step of depositing a plurality of nanoparticles having conductivity and light transmittance on the lower structure, In order to form a network of nanowires having junctions electrically connected at overlapping portions and partitioning the space without the nanowires, the nanowires are formed on the plurality of conductive and light transmissive nanoparticles. Depositing a layer. At least some of the plurality of conductive and light transmissive nanoparticles at least partially fill the plurality of spaces and form additional conductive paths to the network of nanowires across the spaces. The network of nanowires and the plurality of nanoparticles having electrical conductivity and light permeability form at least a part of the light transmissive electrode of the electro-optical device.

  Further objects and advantages of the present invention will become apparent upon consideration of the detailed description, drawings and examples of the invention.

FIG. 1 is a schematic diagram of an electro-optical device according to an embodiment of the present invention.

FIG. 2 shows the light transmittance of an ITO NP-AgNW composite film having a structure of AgNW / ITO NP and ITO NP / AgNW / ITO NP deposited on glass according to an embodiment of the present invention.

FIG. 3 shows a conventional CuIn (Se, S) ₂ device (left), a device having an AgNW / ITO NP transparent conductor according to an embodiment of the present invention (center), and an ITO NP according to an embodiment of the present invention. The apparatus schematic of the apparatus (right) which has a / AgNW / ITO NP transparent conductor is shown.

FIG. 4 shows a cross-sectional scanning electron microscope image of a CISS device having ITO NP / AgNW / ITO NP (left) and AgNW / ITO NP (right) as transparent conductors according to an embodiment of the present invention.

FIG. 5 shows the current density-voltage characteristics of the devices produced in batch 1 (left) and batch 2 (right) for comparing the device according to some embodiments of the present invention with a conventional (control) device. Show.

  Several embodiments of the invention are described in detail below. In describing embodiments of the present invention, specific terminology is used in order to ensure clarity. However, the present invention is not intended to be limited to such specific selected technical terms. Those skilled in the relevant art will recognize that other equivalent members can be applied and that other methods can be developed without departing from the broad concepts of the present invention. All references cited herein, including the prior art and detailed description of the invention, are incorporated so that each is incorporated independently.

  As used herein, the term “light transmissive” means that for a particular application, a sufficient amount of light within the operating wavelength range can pass.

  As used herein, the term “light” shall have a broad meaning including both visible and non-visible regions of the electromagnetic spectrum. For example, infrared light and ultraviolet light are included in the broad sense of the term “light”.

  As used herein, the term “nanowire” refers to conductivity having a cross-sectional dimension of less than 200 nanometers (hereinafter referred to as “nm”) and a longitudinal dimension of at least 10 times the maximum cross-sectional dimension. Including any structure it has. In some cases, the longitudinal dimension may be 100 times or more, 1000 times or more, or more than the maximum cross-sectional dimension.

  As used herein, the term “nanoparticle” is intended to include any shape having all outer dimensions of less than 200 nm.

  As used herein, the term “network of nanowires” refers to an array of nanowires having multiple junctions where different nanowires overlap. The nanowires constituting the nanowire network may be arranged randomly or semi-randomly, and may have a length distribution. That is, the nanowires constituting the nanowire network need not be uniform in length. Nanowire networks are not systematically interwoven or bonded, but are considered to be similar to textiles. As an electrode, a plurality of such nanowires in a network of nanowires form a large number of electrical paths connecting one end and the other end of the network, and even if a relatively small number of joints are broken, Another electrical path that connects the other ends remains. Thus, the nanowire network has both defect resistance and flexibility, and shows some similarity to a communication network such as the Internet.

  As used herein, the term “solution” has a broad meaning including both components dissolved in a liquid and components suspended in a liquid. For example, nanoparticles and / or nanowires suspended in a liquid are considered herein to be included in the definition of the term “solution”.

  FIG. 1 is a schematic view of an electro-optical device 100 according to another embodiment of the present invention. The electro-optical device 100 has a joint structure electrically connected at the overlapping portion of the lower structure 102 and the nanowire, and forms a network of nanowires that partitions the space without the nanowire deposited on the lower structure 102. In order to do so, a layer of nanowires 104 deposited on the lower structure 102 and a plurality of the spaces arranged to at least partially fill the space and further conducting paths to the network of nanowires across the spaces And a plurality of nanoparticles 106 attached to the network of nanowires 104. FIG. 1 only depicts several nanowires 104 and several multiple nanoparticles 106 as examples. In some embodiments, the plurality of nanoparticles fuses overlapping nanowire junctions, such as junction 108, to reduce the sheet electrical resistance of the nanowire network. The layer of the nanowire 104 and the plurality of nanoparticles 106 having conductivity and light transmission form at least a part of the light transmission electrode of the electro-optical device 100.

  In some embodiments, the plurality of electrically conductive and light transmissive nanoparticles 106 substantially fills the space free of the nanowires. In some embodiments, at least some of the plurality of electrically conductive and light transmissive nanoparticles 106 fuse together overlapping nanowire joints, such as joints 108, to form a sheet of a network of nanowires 104. Reduce electrical resistance.

  In some embodiments, the electro-optic device 100 further comprises a layer of adhesive material 110 over the network of nanowires 104, over the plurality of nanoparticles 106, and over the substructure 102. An agent material 110 encapsulates a network of nanowires 104 and a plurality of nanoparticles 106 on the substructure 102.

  In some embodiments, the substructure 102 can further include a layer of conductive and light transmissive nanoparticles (not shown in FIG. 1), and the layer of nanowires 104 can include the substructure. Are deposited on a layer of nanoparticles having electrical conductivity and optical transparency. The general concept of the present invention can include multiple layers of any combination of electrically conductive and light transmissive nanoparticles and / or nanowires. However, each layer of nanowires needs to be in contact with at least one layer of nanoparticles having electrical conductivity and optical transparency.

  In some embodiments, the plurality of electrically conductive and light transmissive nanoparticles 106 can include at least one of a metal oxide, a conductive polymer, or fluorine-doped tin oxide. In some embodiments, the plurality of electrically conductive and light transmissive nanoparticles 106 is a group of metal oxides comprising indium tin oxide, zinc oxide, aluminum-doped zinc oxide, indium zinc oxide, and cerium oxide. At least one metal oxide selected from: In some embodiments, the network of nanowires 104 can include at least one of carbon nanotubes or metal nanowires. In some embodiments, the metal nanowire can include at least one of silver, gold, copper, or aluminum. In some embodiments, the nanowire may be, for example, a substantially pure element material, or may be a doped alloy or metal alloy. In some embodiments, the network of nanowires 104 can consist essentially of silver nanowires, and the plurality of electrically conductive and light transmissive nanoparticles 106 are substantially indium tin oxide nanoparticles. Can consist of In some embodiments, the substructure 102 can include an active layer, and the electro-optic device is at least one of a photovoltaic device, a light emitting diode, or a photodiode. However, the general concept of the invention is not limited to these examples. Any electro-optic (or optoelectronic) device comprising a layer having electrical conductivity and at least partial light transmission may be included in the general concept of the invention.

  The method for manufacturing the electro-optical device 100 according to the embodiment of the present invention includes a step of preparing the lower structure 102, a joint portion electrically connected at the overlapping portion of the nanowires, and a space where the nanowires 104 are absent. Depositing a layer of nanowires 104 on the underlying structure 102 to form a network of nanowires to perform, and a plurality of said conductive paths to form additional conductive paths for the network of nanowires across the space Depositing a plurality of electrically conductive and light transmissive nanoparticles 106 on the underlying structure 102 and nanowire 104 layers to at least partially fill the space. The network of nanowires 104 and the plurality of nanoparticles having electrical conductivity and light permeability form at least a part of the light transmissive electrode of the electro-optical device. In the manufacturing method according to some embodiments of the present invention, the various materials described above can be used.

  In some embodiments, the method of manufacturing an electro-optic device deposits a layer of conductive and light transmissive nanoparticles on a portion of the lower structure 102 before the step of preparing the lower structure 102. The substructure 102 includes a layer of nanoparticles having electrical conductivity and light transmission. In this embodiment, the step of depositing the nanowire 104 layer on the lower structure 102 is to deposit the nanowire layer on the conductive and light transmissive nanoparticle layer.

  In some embodiments, the method of manufacturing the electro-optical device 100 includes at least one of depositing a layer of nanowires 104 or depositing the plurality of nanoparticles 106 having electrical conductivity and optical transparency. An annealing step can be further included after the one. In some embodiments, the annealing step may be performed at a temperature of at least 25 ° C. and less than 1000 ° C.

  In some embodiments, the method of manufacturing the electro-optic device 100 includes at least one of depositing a layer of nanowires 104 or depositing a plurality of nanoparticles having the electrical conductivity and light transmission properties. After the two, a step of curing by ultraviolet irradiation can be further included.

  The following examples serve to illustrate the concept of the present invention, but the general concept of the present invention is not limited by such specific examples.

  Sputter deposited indium tin oxide (ITO) or aluminum doped zinc oxide is commonly used as a transparent conductor for thin film electro-optic devices such as displays and thin film solar cells. This is because these membranes provide both low resistance and high permeability (C. A. Hoel, T. O. Mason, J.-F. Gaillard, and K. R. Poeppelmeier, Chem. Mater. 2010, 22, 3569). The manufacturing cost of conventional transparent conductors is high due to the use of vacuum technology, so non-vacuum processing methods have been studied for the purpose of reducing costs (RG Gordon, MRS). bulletin 2000, 25, 52). Although solution-processed silver nanowires (AgNW) have been explored as a possible alternative, these films have shown poor adhesion to adjacent layers (S. De, TM Higgins, PE Lyons, EM Doherty , PN Nirmalraj, WJ Blau, JJ Boland, ACS Nano 2009, 3, 1767). Accordingly, there is a need for the development of new structures or materials that provide excellent adhesion properties as well as electro-optic properties.

According to an embodiment of the present invention, the ITO nanoparticle (NP) -AgNW film is produced using a solution process and employed as a transparent conductor in CuIn (Se, S) ₂ (or CISS) solar cells. . The results of the examples demonstrate that the ITO NP-AgNW film exhibits excellent adhesion and electro-optic properties comparable to conventional sputter deposited ITO. In addition, ITO NP-AgNW films have been shown to be suitable as transparent conductors (or window layers) for CISS solar cells, and performance for some embodiments has been used in conventional CISS devices. Even better than sputter deposited ITO films. To our knowledge, this is the first demonstration of the use of an ITO NP-AgNW composite film as a transparent conductor.

Experiment and Results Fabrication of ITO nanoparticle-AgNW composite transparent conductor.
The alcohol-based AgNW solution was spin-cast to form a film on the glass substrate. Thereafter, an ITO NP solution was spin-cast from the alcohol-based dispersion onto the AgNW layer. Polyvinyl alcohol dissolved in deionized (DI) water was added to the ITO particle solution as needed to improve the adhesion of the ITO NP-AgNW film. In order to further improve the adhesion of the ITO NP-AgNW film to the substrate, an ITO NP film was inserted as needed between the substrate and the AgNW layer. The ITO NP layer and the AgNW layer were deposited by spin coating from an alcohol-based solution with a rotation speed of 2000 rpm, and the deposited film was then annealed at a temperature of 120 ° C.

Electrical and optical properties of ITO-AgNW composite film.
FIG. 2 shows the light transmittance of an ITO NP-AgNW composite film having a structure of AgNW / ITO NP and ITO NP / AgNW / ITO NP deposited on glass. The sheet resistance of these films is 32Ω / □ and 24Ω / □, respectively. Both films have a light transmittance in the visible region of about 80-90%.

CuIn (Se, S) ₂ device with ITO NP-AgNW composite film as transparent conductor.
Our CISS device is described in the literature (I. Repins, MA Contreras, B. Egaas, C. DeHart, J. Scharf, CL Perkins, B. To, R. Noufi, Prog. Photovolt. Res. Appl. 2008, 16, 235) and manufactured according to the general high-efficiency structure reported in 235). The controller architecture is based on a soda lime glass substrate on which is subsequently deposited a layer of CuInSe ₂ , cadmium sulfide, sputtered intrinsic zinc oxide, and sputter deposited ITO film. In our apparatus according to embodiments of the present invention, sputter deposited i-ZnO and ITO are replaced with solution-processed ITO NP-AgNW composite films. Each version of the device structure is shown in FIG.

  FIG. 4 shows two cross-sectional scanning electron microscope images of a CISS device having ITO NP / AgNW / ITO NP as a transparent conductor. As can be seen in the image, the film is continuous across the CdS layer and is composed of a large number of dense nanoparticles (NP) approximately 50 nm in diameter.

  The working device was manufactured using an ITO NP-AgNW composite layer by solution process similar to that shown in FIG. These devices showed higher efficiencies than control devices with sputter deposited i-ZnO / ITO as the transparent conductor layer. FIG. 5 shows the current density-voltage characteristics of a typical device having an ITO NP-AgNW layer by a solution process.

Advantages of solution-processed ITO NP-AgNW composite layers according to some embodiments of the present invention stem from, for example, non-vacuum fabrication production, high-throughput deposition methods, and low process temperatures Can do. Compared to common window layers deposited by sputtering or chemical vapor deposition, solution-processed ITO NP-AgNW films can provide a significant reduction in processing costs, thus sacrificing transparent conductor adhesion and electro-optic properties. Without increasing the likelihood of cost-effective device manufacturing. Unique to CuInSe ₂ solar cells, but when trying to avoid damage to either the absorbing material or the thermally unstable cadmium sulfide buffer layer placed just before the window layer in the device The low process temperature and good chemical conditions associated with this type of transparent conductor and deposition technique are extremely useful.

Some aspects of the invention can include, but are not limited to, the following:
1. But not limited to _{Cu (In, Ga) (Se} , S) 2, Cu 2 ZnSn (Se, S) 4, CdTe, silicon solar cells, organic solar cells, organic light emitting diodes, and an inorganic light-emitting diodes, displays Use ITO NP-AgNW film by solution process as part or all of the transparent conductor and / or metal grid in electro-optical devices such as solar cells.
2. Item 1 (above) characterized in that the composite film comprises a multilayer film of ITO NP / AgNW / ITO NP.
3. Item 1 (above) characterized in that the composite film comprises a multilayer film of AgNW / ITO NP.
4). Item 1 (above) characterized in that the composite film comprises a multilayer film of ITO NP / AgNW.
5. The feature of item 1 (above), wherein the composite film consists of a network of ITO NP-AgNW made with a mixed ITO NP-AgNW solution.
6). ITO NP-AgNW film is a non-vacuum method such as spin-coating, doctor blading, rod-coating, slit-coating, and spray coating Features of item 1 (above) produced by various methods.
7). The feature of item 1 (above), wherein the ITO particle size is between 1 nm and 1000 nm.
8). Item 1 (above) in which polymer materials such as polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, and polyvinyl butyral used to form the ITO NP-AgNW composite film are added to the ITO NP solution and / or AgNW solution. Feature.
9. The feature of item 1 (above), wherein the AgNW length is between 100 nm and 1000 um.
10. Other metal oxides including, but not limited to, zinc oxide, aluminum doped zinc oxide, indium zinc oxide, cerium oxide, and fluorine doped tin oxide, and conductive polymers including but not limited to PEDOT: PSS, The feature of item 1 (above), which is a candidate for performing the same function as ITO NP.
11. Other one-dimensional nanostructures including, but not limited to, carbon nanotubes and metal nanowires including copper, gold, and aluminum and / or their alloy nanowires are also candidates for performing the same function as AgNW 1 Features of (above).
12 The feature of item 1 (above) wherein the film is annealed at a temperature in the range of 25-1000 ° C.
13. A feature of item 1 (above) in which the film is cured by UV irradiation.

  The embodiments described and discussed herein are intended only to teach those skilled in the art how to make and use the invention. In describing embodiments of the present invention, specific terminology is used in order to ensure clarity. However, the present invention is not intended to be limited to such specific selected technical terms. The above-described embodiments of the present invention may be modified and changed without departing from the present invention, as will be appreciated by those skilled in the art in view of the above techniques. Therefore, within the scope of the appended claims and equivalents thereof, the present invention may be practiced otherwise than as specifically described.

DESCRIPTION OF SYMBOLS 100 Electro-optical device 102 Substructure 104 Nanowire 106 Nanoparticle 108 Joint part 110 Adhesive material

Claims (35)

Substructure,
A layer of nanowires deposited on the substructure to form a network of nanowires having junctions electrically connected at the overlapping portions of the nanowires and defining a space free of the nanowires;
A plurality of nanoparticles having electrical conductivity and optical transparency arranged to at least partially fill the plurality of spaces and forming a further conductive path for the network of nanowires across the spaces. An electro-optic device,
The electro-optic device, wherein the nanowire network and the plurality of nanoparticles having electrical conductivity and light permeability form at least part of a light-transmissive electrode of the electro-optic device.   The electro-optical device according to claim 1, wherein the plurality of nanoparticles having conductivity and light transmittance substantially fill the space without the nanowire.   2. The sheet electrical resistance of the network of nanowires according to claim 1, wherein at least some of the plurality of conductive and light transmissive nanoparticles fuses overlapping nanowire junctions to reduce sheet electrical resistance of the nanowire network. The electro-optical device described.   The substructure further includes a nanoparticle layer having electrical conductivity and light transmission, and the nanowire layer is deposited on the nanoparticle layer having electrical conductivity and light transmission. The electro-optical device according to claim 1.   Encapsulating at least one of the nanowire layer and the plurality of nanoparticles having electrical conductivity and light transmission, or the nanowire layer and the plurality of nanoparticles having electrical conductivity and light transmission The electro-optical device according to claim 1, further comprising a polymer layer in which at least one of the layers is mixed to form a composite polymer-nanowire-nanoparticle layer.   2. The electro-optical device according to claim 1, wherein the plurality of nanoparticles having conductivity and light transmittance include at least one of a metal oxide, a conductive polymer, or fluorine-doped tin oxide. .   The at least one metal selected from the group consisting of metal oxides, wherein the plurality of nanoparticles having electrical conductivity and optical transparency are selected from the group consisting of indium tin oxide, zinc oxide, aluminum-doped zinc oxide, indium zinc oxide, and cerium oxide. The electro-optical device according to claim 6, further comprising an oxide.   The electro-optical device according to claim 1, wherein the network of nanowires includes at least one of carbon nanotubes or metal nanowires.   The electro-optical device according to claim 8, wherein the metal nanowire includes at least one of silver, gold, copper, and aluminum.   The electro-optical device according to claim 6, wherein the network of nanowires includes at least one of carbon nanotubes or metal nanowires.   The electro-optical device according to claim 10, wherein the metal nanowire includes at least one of silver, gold, copper, and aluminum.   The at least one metal selected from the group consisting of metal oxides, wherein the plurality of nanoparticles having electrical conductivity and optical transparency are selected from the group consisting of indium tin oxide, zinc oxide, aluminum-doped zinc oxide, indium zinc oxide, and cerium oxide. The electro-optical device according to claim 11, comprising an oxide. The network of nanowires consists essentially of silver nanowires,
The electro-optical device according to claim 1, wherein the plurality of nanoparticles having conductivity and light transmittance are substantially composed of nanoparticles of indium tin oxide.   The electro-optical device according to claim 1, wherein the lower structure includes an active layer, and the electro-optical device is at least one of a photovoltaic device, a light-emitting diode, or a photodiode. Preparing a substructure;
Depositing a layer of nanowires on the underlying structure to form a network of nanowires having junctions electrically connected at the overlapping portions of the nanowires and defining a space free of the nanowires;
In order to form a further conductive path for the network of nanowires traversing the space, a plurality of conductive and light transmissive nanoparticles are applied to the lower portion so as to at least partially fill the plurality of spaces. A structure and a step of depositing on the nanowire layer, comprising:
The method of manufacturing an electro-optical device, wherein the nanowire network and the plurality of conductive and light-transmitting nanoparticles form at least a part of a light-transmitting electrode of the electro-optical device. Before the step of preparing the substructure, the method further comprises the step of depositing a layer of nanoparticles having electrical conductivity and light transmission on a part of the substructure, so that the substructure is electrically conductive. And a layer of nanoparticles having optical transparency,
The step of depositing the nanowire layer on the substructure comprises depositing the nanowire layer on the conductive and light transmissive nanoparticle layer. 15. A method for manufacturing the electro-optical device according to 15.   16. The method of manufacturing an electro-optical device according to claim 15, wherein the plurality of nanoparticles having conductivity and light transmittance substantially fill the space without the nanowire.   16. The at least some of the plurality of conductive and light transmissive nanoparticles fuses overlapping nanowire junctions to reduce sheet electrical resistance of the nanowire network. A method of manufacturing the electro-optical device according to claim.   The method of manufacturing an electro-optical device according to claim 15, further comprising a step of adding a plurality of nanowires to a liquid to form a nanowire solution for solution deposition of the nanowire layer.   Forming a nanoparticle solution for solution deposition of the plurality of electrically conductive and light transmissive nanoparticles by further adding a plurality of electrically conductive and light transmissive nanoparticles to the liquid. The method of manufacturing an electro-optical device according to claim 19.   21. The electro-optic device according to claim 20, further comprising a step of mixing a polymer with at least one of the nanowire solution or the nanoparticle solution to form a composite layer containing the polymer. Method.   The electro-optical device according to claim 15, wherein the plurality of conductive and light-transmitting nanoparticles include at least one of a metal oxide, a conductive polymer, or fluorine-doped tin oxide. Manufacturing method.   The at least one metal selected from the group consisting of metal oxides, wherein the plurality of nanoparticles having electrical conductivity and optical transparency are selected from the group consisting of indium tin oxide, zinc oxide, aluminum-doped zinc oxide, indium zinc oxide, and cerium oxide. The method of manufacturing an electro-optical device according to claim 22, comprising an oxide.   The method of manufacturing an electro-optical device according to claim 15, wherein the network of nanowires includes at least one of carbon nanotubes or metal nanowires.   25. The method of manufacturing an electro-optical device according to claim 24, wherein the metal nanowire includes at least one of silver, gold, copper, and aluminum.   23. The method of manufacturing an electro-optical device according to claim 22, wherein the network of nanowires includes at least one of a carbon nanotube or a metal nanowire.   27. The method of manufacturing an electro-optical device according to claim 26, wherein the metal nanowire includes at least one of silver, gold, copper, and aluminum.   The at least one metal selected from the group consisting of metal oxides, wherein the plurality of nanoparticles having electrical conductivity and optical transparency are selected from the group consisting of indium tin oxide, zinc oxide, aluminum-doped zinc oxide, indium zinc oxide, and cerium oxide. 28. The method of manufacturing an electro-optical device according to claim 27, comprising an oxide. The network of nanowires consists essentially of silver nanowires,
16. The method of manufacturing an electro-optical device according to claim 15, wherein the plurality of nanoparticles having electrical conductivity and light transmittance are substantially composed of indium tin oxide nanoparticles.   The electro-optical device manufacturing method according to claim 15, wherein the lower structure includes an active layer, and the electro-optical device is at least one of a photovoltaic device, a light emitting diode, or a photodiode. Method.   The method further comprises annealing after at least one of the step of depositing the layer of nanowires or the step of depositing the plurality of conductive and light transmissive nanoparticles. Item 16. A method for manufacturing the electro-optical device according to Item 15.   32. The method of manufacturing an electro-optical device according to claim 31, wherein the annealing step is performed at a temperature of at least 25 [deg.] C. and less than 1000 [deg.] C.   The method further comprises the step of curing by ultraviolet irradiation after at least one of the step of depositing the nanowire layer, or the step of depositing the plurality of conductive and light transmissive nanoparticles. The method of manufacturing an electro-optical device according to claim 15.   The method further comprises the step of curing by ultraviolet irradiation after at least one of the step of depositing the nanowire layer, or the step of depositing the plurality of conductive and light transmissive nanoparticles. A method for manufacturing an electro-optical device according to claim 32. Preparing a substructure;
Depositing a plurality of conductive and light transmissive nanoparticles on the substructure;
In order to form a network of nanowires that have joints electrically connected at the overlapping portions of the nanowires and define a space without the nanowires, the conductive and light transmissive nanoparticles are formed on the nanowires. Depositing a layer of nanowires, and a method of manufacturing an electro-optical device comprising:
At least some of the plurality of electrically conductive and light transmissive nanoparticles at least partially fill the plurality of spaces and form additional conductive paths to the network of nanowires across the spaces;
The method of manufacturing an electro-optical device, wherein the nanowire network and the plurality of conductive and light-transmitting nanoparticles form at least a part of a light-transmitting electrode of the electro-optical device.